An ab initio study of the structure and vibrational spectra of allyl and 1,4-pentadienyl radicals

P. Szalay, A. Császár, G. Fogarasi, A. Karpfen, H. Lischka

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

MCSCF and MR-ACPF calculations on the structure and vibrational frequencies of allyl (2-propenyl) and 1,4-pentadienyl radicals are presented. Using different levels of theory the instability problem in allyl has been investigated in great detail. Based on these conclusions fully optimized structures and force constants were calculated at the three-orbital CAS-MCSCF and at the MR-ACPF level for allyl. To correct for systematic errors, an empirical scaling was also applied on the MCSCF force field. The scaled MCSCF and the unadjusted MR-ACPF force constants were used to calculate the vibrational frequencies. A reassignation of the experimental infrared spectrum is also given. Using the scale factors optimized for allyl the scaled MCSCF force field and vibrational frequencies of pentadienyl were also calculated.

Original languageEnglish
Pages (from-to)1246-1256
Number of pages11
JournalThe Journal of Chemical Physics
Volume93
Issue number2
Publication statusPublished - 1990

Fingerprint

Vibrational spectra
vibrational spectra
field theory (physics)
Systematic errors
systematic errors
infrared spectra
Infrared radiation
scaling
orbitals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

An ab initio study of the structure and vibrational spectra of allyl and 1,4-pentadienyl radicals. / Szalay, P.; Császár, A.; Fogarasi, G.; Karpfen, A.; Lischka, H.

In: The Journal of Chemical Physics, Vol. 93, No. 2, 1990, p. 1246-1256.

Research output: Contribution to journalArticle

@article{1ef364c8376043c7a2b148a6957a17f8,
title = "An ab initio study of the structure and vibrational spectra of allyl and 1,4-pentadienyl radicals",
abstract = "MCSCF and MR-ACPF calculations on the structure and vibrational frequencies of allyl (2-propenyl) and 1,4-pentadienyl radicals are presented. Using different levels of theory the instability problem in allyl has been investigated in great detail. Based on these conclusions fully optimized structures and force constants were calculated at the three-orbital CAS-MCSCF and at the MR-ACPF level for allyl. To correct for systematic errors, an empirical scaling was also applied on the MCSCF force field. The scaled MCSCF and the unadjusted MR-ACPF force constants were used to calculate the vibrational frequencies. A reassignation of the experimental infrared spectrum is also given. Using the scale factors optimized for allyl the scaled MCSCF force field and vibrational frequencies of pentadienyl were also calculated.",
author = "P. Szalay and A. Cs{\'a}sz{\'a}r and G. Fogarasi and A. Karpfen and H. Lischka",
year = "1990",
language = "English",
volume = "93",
pages = "1246--1256",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "2",

}

TY - JOUR

T1 - An ab initio study of the structure and vibrational spectra of allyl and 1,4-pentadienyl radicals

AU - Szalay, P.

AU - Császár, A.

AU - Fogarasi, G.

AU - Karpfen, A.

AU - Lischka, H.

PY - 1990

Y1 - 1990

N2 - MCSCF and MR-ACPF calculations on the structure and vibrational frequencies of allyl (2-propenyl) and 1,4-pentadienyl radicals are presented. Using different levels of theory the instability problem in allyl has been investigated in great detail. Based on these conclusions fully optimized structures and force constants were calculated at the three-orbital CAS-MCSCF and at the MR-ACPF level for allyl. To correct for systematic errors, an empirical scaling was also applied on the MCSCF force field. The scaled MCSCF and the unadjusted MR-ACPF force constants were used to calculate the vibrational frequencies. A reassignation of the experimental infrared spectrum is also given. Using the scale factors optimized for allyl the scaled MCSCF force field and vibrational frequencies of pentadienyl were also calculated.

AB - MCSCF and MR-ACPF calculations on the structure and vibrational frequencies of allyl (2-propenyl) and 1,4-pentadienyl radicals are presented. Using different levels of theory the instability problem in allyl has been investigated in great detail. Based on these conclusions fully optimized structures and force constants were calculated at the three-orbital CAS-MCSCF and at the MR-ACPF level for allyl. To correct for systematic errors, an empirical scaling was also applied on the MCSCF force field. The scaled MCSCF and the unadjusted MR-ACPF force constants were used to calculate the vibrational frequencies. A reassignation of the experimental infrared spectrum is also given. Using the scale factors optimized for allyl the scaled MCSCF force field and vibrational frequencies of pentadienyl were also calculated.

UR - http://www.scopus.com/inward/record.url?scp=0001695167&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001695167&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001695167

VL - 93

SP - 1246

EP - 1256

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 2

ER -